WO1997032816A1 - Adsorbent for cesium ion and method of making and using - Google Patents

Adsorbent for cesium ion and method of making and using Download PDF

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Publication number
WO1997032816A1
WO1997032816A1 PCT/US1996/011487 US9611487W WO9732816A1 WO 1997032816 A1 WO1997032816 A1 WO 1997032816A1 US 9611487 W US9611487 W US 9611487W WO 9732816 A1 WO9732816 A1 WO 9732816A1
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Prior art keywords
particles
kcohex
web
spherical
enmeshed
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PCT/US1996/011487
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English (en)
French (fr)
Inventor
Lloyd R. White
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Minnesota Mining And Manufacturing Company
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Publication date
Application filed by Minnesota Mining And Manufacturing Company filed Critical Minnesota Mining And Manufacturing Company
Priority to AU71035/96A priority Critical patent/AU7103596A/en
Priority to EP19960932136 priority patent/EP0885169B1/en
Priority to JP53173797A priority patent/JP2000506827A/ja
Priority to DE69608820T priority patent/DE69608820T2/de
Publication of WO1997032816A1 publication Critical patent/WO1997032816A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016Particle form
    • B01J20/28019Spherical, ellipsoidal or cylindrical
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01CAMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C3/00Cyanogen; Compounds thereof
    • C01C3/08Simple or complex cyanides of metals
    • C01C3/12Simple or complex iron cyanides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0225Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
    • B01J20/0229Compounds of Fe
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004Sorbent size or size distribution, e.g. particle size
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28028Particles immobilised within fibres or filaments
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/2803Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28033Membrane, sheet, cloth, pad, lamellar or mat
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078Pore diameter
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/3078Thermal treatment, e.g. calcining or pyrolizing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/3085Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01DCOMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D17/00Rubidium, caesium or francium compounds
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10Obtaining alkali metals
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • C22B3/24Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/42Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
    • GPHYSICS
    • G21NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21FPROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/007Recovery of isotopes from radioactive waste, e.g. fission products
    • GPHYSICS
    • G21NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21FPROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04Treating liquids
    • G21F9/06Processing
    • G21F9/12Processing by absorption; by adsorption; by ion-exchange
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/30Particle morphology extending in three dimensions
    • C01P2004/32Spheres
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/51Particles with a specific particle size distribution
    • C01P2004/52Particles with a specific particle size distribution highly monodisperse size distribution
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/61Micrometer sized, i.e. from 1-100 micrometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/60Optical properties, e.g. expressed in CIELAB-values
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S159/00Concentrating evaporators
    • Y10S159/15Special material
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/249921Web or sheet containing structurally defined element or component
    • Y10T428/249953Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249986Void-containing component contains also a solid fiber or solid particle
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2508Coating or impregnation absorbs chemical material other than water

Definitions

  • the present invention pertains to substantially spherical, monodisperse particles of potassium cobalt hexacyanoferrate and a method therefor, and a method of using the particles in loose form, in a column, or enmeshed in a porous web for extraction of cesium, particularly radioactive cesium (Cs), from solution
  • Cs radioactive cesium
  • Potassium cobalt hexacyanoferrate is known in the art as an effective adsorbent for cesium ions and has found important use in removing radioactive cesium ions from nuclear wastes via an ion exchange process
  • the method has been described, for example, in U S Patent No 3,296, 123, in "A Review of Information on Ferrocyanate Solids for Removal of Cesium from Solutions,” P A Haas, Sep. Sa. Technol. 28 (17-18), 2479-2508 ( 1993), and in “Evaluation of Selected Ion Exchangers for the Removal of Cesium and Strontium from MVST W-25 Supernate," J L Collins, et al , ORNL/TM- 12938, April 1995, and references cited therein
  • Granular potassium cobalt hexacyanoferrate hereinafter referred to as "KCOHEX”
  • KCOHEX Granular potassium cobalt hexacyanoferrate
  • the method of preparing particulate KCOHEX suffers from two significant drawbacks First, grinding the dried solids must be done carefully so as to minimize formation of unusable fines Second, since a wide range of particle sizes results from grinding, the particulate must be sized through sieves These operations are time-consuming and inevitably cause loss of product
  • sized KCOHEX is then loaded into columns in order to remove cesium from radioactive waste solutions
  • columns of up to 60 cm in length and 14 cm in diameter have been used, and flow rates of 80 L/h have been achieved
  • Spray-drying of solid materials is a method known in the art for preparation of useful solids See, for example, Kirk-Othmer Encyclopedia of Chemical
  • the present invention provides a method comprising the step of spray-drying a slurry of potassium cobalt hexacyanoferrate (KCOHEX) particles to provide monodisperse, substantially spherical KCOHEX particles
  • the method further comprises the step of heating the spherical KCOHEX particles until their color changes from green to purplish-black.
  • the spherical KCOHEX particles can be used in columns or beds to selectively remove Cs ions from aqueous solutions.
  • the loose KCOHEX particles can be introduced into a
  • the spherical KCOHEX particles can be enmeshed in porous, nonwoven, fibrous webs.
  • the webs can be used in solid phase extraction (SPE) procedures to selectively remove Cs ions from aqueous solutions
  • the invention provides an SPE device comprising a pleated porous, fibrous non-woven SPE web comprising spherical, monodisperse potassium cobalt hexacyanoferrate particulate and poly(m- or p-terephthalamide) fibers enclosed in a cartridge device
  • the invention provides a method of removing cesium ions from an aqueous solution comprising passing the aqueous solution through a porous, fibrous non-woven SPE web comprising spherical, monodisperse potassium cobalt hexacyanoferrate particulate
  • the invention provides a method of removing cesium ions from an aqueous solution comprising passing the aqueous solution through an SPE column comprising spherical, monodisperse potassium cobalt hexacyanoferrate particulate
  • size means the diameter of a spherical particle
  • monodisperse means a monomodal particle size distribution having a range of up to about 500 micrometers, preferably about 60 micrometers, and
  • drain time means the time required to dewater a slurry of particles and fibers when making a sheet
  • the advantages of the particles of the invention include reduced drain time by a factor of at least two compared to non-spherical, irregularly shaped, prior art particles typically obtained from a grinding process, when making a sheet article Further, the overall process yield in making a sheet article comprising the particles of the invention is 80-90 percent or more compared to a yield of about 60 percent when using prior art ground and sieved particles.
  • free-flowing spherical particles will pack more uniformly in columns, resulting in less channeling during extraction compared with irregularly shaped prior art KCOHEX particles
  • spherical KCOHEX particles can be prepared by mixing at 0° to 5°C an aqueous solution of potassium ferrocyanide (available from Aldrich Chemical Co., and many other suppliers) with an aqueous solution of cobalt nitrate, buffered to a pH of 5-6 using acetic acid as the buffering agent.
  • the immediately formed precipitate of KCOHEX is collected and thoroughly washed with water
  • the wet KCOHEX precipitate which comprises particles of irregular shapes is slurried with liquid, preferably water, and then spray-dried preferably using a spinning disk atomizer and collecting the resulting substantially spherical KCOHEX particles having a size in the range of about 1 to 500 micrometers, preferably about 1 to 60 micrometers, more preferably 5 to 15 micrometers, with a most preferred average size of about 9 to 12 micrometers
  • the spherical KCOHEX particles are then heated until the color changes from green to purplish black but the particle size
  • the slurry preferably has a solids content of less than 8 percent by weight, more preferably 7 5 percent by weight, to ensure smooth operation of the apparatus
  • the particles After spray-drying, the particles are dark green in color; they are free- flowing with most preferred average diameters in the range of 9-12 micrometers
  • the particles of the invention can be enmeshed in various porous, fibrous, nonwoven webs or matrices
  • Types of webs or matrices include fibrillated polytetrafluoroethylene (PTFE), microfibrous webs, macrofibrous webs, and polymer pulps
  • the PTFE composite sheet material of the invention is prepared by blending the particulate or combination of particulates employed with a PTFE emulsion until a uniform dispersion is obtained and adding a volume of process lubricant up to approximately one half the volume of the blended particulate Blending takes place along with sufficient process lubricant to exceed sorptive capacity of the particles in order to generate the desired porosity level of the resultant article
  • Preferred process lubricant amounts are in the range of 3 to 200 percent by weight in excess of that required to saturate the particulate, as is disclosed in U S Patent No 5,071,610
  • the aqueous PTFE dispersion is then blended with the particulate mixture to form a mass having a putty-like or dough-like consistency
  • the sorptive capacity of the solids of the mixture is noted to have been exceeded when small amounts of water can no longer be incorporated into the mass without separation This condition should be maintained throughout the entire mixing operation
  • the putty-like mass is then subjecte
  • Devices employed for obtaining the necessary intensive mixing are commercially available intensive mixing devices which are sometimes referred to as internal mixers, kneading mixers, double-blade batch mixers as well as intensive mixers and twin screw compounding mixers
  • the most popular mixer of this type is the sigma-blade or sigma-arm mixer
  • Some commercially available mixers of this type are those sold under the common designations Banbury mixer, Mogul mixer, C W Brabender Prep mixer and C W Brabender sigma blade mixer
  • Other suitable intensive mixing devices may also be used
  • the soft putty-like mass is then transferred to a calendering device where the mass is calendered between gaps in calendering rolls preferably maintained at a temperature up to 125°C, preferably in the range of 0° to about 100°C, more preferably in the range of 20°C to 60°C, to cause additional fibrillation of the PTFE particles of the mass, and consolidation while maintaining the water level of the mass at least at a level of near the sorptive capacity of the solids, until sufficient fibrillation occurs to produce the desired extraction medium
  • the calendering rolls are made of a rigid material such as steel
  • a useful calendering device has a pair of rotatable opposed calendering rolls each of which may be heated and one of which may be adjusted toward the other to reduce the gap or nip between the two Typically, the gap is adjusted to a setting of 10 millimeters for the initial pass of the mass and, as calendering operations progress, the gap is reduced until adequate consolidation occurs At the end of the initial
  • the lubricant level of the mass is maintained at least at a level of exceeding the absorptive capacity of the solids by at least 3 percent by weight, until sufficient fibrillation occurs and to produce porosity or void volume of at least 30 percent and preferably 40 to 70 percent of total volume.
  • the preferred amount of lubricant is determined by measuring the pore size of the article using a Coulter Porometer as described in the Examples below. Increased lubricant results in increased pore size and increased total pore volume as is disclosed in U S Patent No. 5,071 ,610.
  • the calendered sheet is then dried under conditions which promote rapid drying yet will not cause damage to the composite sheet or any constituent therein.
  • drying is carried out at a temperature below 200°C
  • the preferred means of drying is by use of a forced air oven
  • the preferred drying temperature range is from 20°C to about 70°C
  • the most convenient drying method involves suspending the composite sheet at room temperature for at least 24 hours. The time for drying may vary depending upon the particular composition, some particulate materials having a tendency to retain water more than others
  • the resultant composite sheet preferably has a tensile strength when measured by a suitable tensile testing device such as an Instron (Canton, MA) tensile testing device of at least 0 5 MPa
  • a suitable tensile testing device such as an Instron (Canton, MA) tensile testing device of at least 0 5 MPa
  • the resulting composite sheet has uniform porosity and a void volume of at least 30 percent of total volume
  • the PTFE aqueous dispersion employed in producing the PTFE composite sheet of the invention is a milky-white aqueous suspension of minute PTFE particles.
  • the PTFE aqueous dispersion will contain about 30 percent to about 70 percent by weight solids, the major portion of such solids being PTFE particles having a particle size in the range of about 0 05 to about 0.5 micrometers
  • the commercially available PTFE aqueous dispersion may contain other ingredients, for example, surfactant materials and stabilizers which promote continued suspension of the PTFE particles
  • TeflonTM 30 and TeflonTM 30B contain about 59 percent of about 61 percent solids by weight which are for the most part 0.05 to 0.5 micrometer PTFE particles and from about 5 5 percent to about 6.5 percent by weight (based on weight of PTFE resin) of non-ionic wetting agent, typically octylphenol polyoxyethylene or nonylphenol polyoxyethylene TeflonTM 42 contains about 32 to 35 percent by weight solids and no wetting agent but has a surface layer of organic solvent to prevent evaporation
  • a preferred source of PTFE is FLUONTM, available from ICI Americas, Inc Wilmington, DE It is generally desirable to remove, by organic solvent extraction, any residual surfactant or wetting agent after formation of the article
  • the fibrous membrane (web) can comprise non-woven, macro- or microfibers preferably selected from the group of fibers consisting of polyamide, polyolefm, polyester, polyurethane, glass fiber, polyvinylhalide, or a combination thereof
  • the fibers preferably are polymeric (If a combination of polymers is used, a bicomponent fiber may be obtained ) If polyvinylhalide is used, it preferably comprises fluorine of at most 75 percent (by weight) and more preferably of at most 65 percent (by weight) Addition of a surfactant to such webs may be desirable to increase the wettability of the component fibers
  • the web can comprise thermoplastic, melt-extruded, large-diameter fibers which have been mechanically-calendered, air-laid, or spunbonded These fibers have average diameters in the general range of 50 ⁇ m to 1 ,000 ⁇ m
  • Such non-woven webs with large-diameter fibers can be prepared by a spunbond process which is well known in the art (See, e g , U S Patent Nos 3,338,992, 3,509,009, and 3,528, 129 )
  • a post-fiber spinning web-consolidation step i e., calendering
  • Non-woven webs made from large-diameter staple fibers can also be formed on carding or air-laid machines (such as a Rando-WebberTM Model 12BS made by Curlator Corp , East Rochester, NY), as is well
  • a binder is normally used to produce self-supporting webs prepared by the air-laying and carding processes and is optional where the spunbond process is used
  • Such binders can take the form of resin systems which are applied after web formation or of binder fibers which are incorporated into the web during the air laying process
  • binder fibers examples include adhesive-only type fibers such as KodelTM 43 UD (Eastman Chemical Products, Kingsport, TN) and bicomponent fibers, which are available in either side-by-side form (e g , Chisso ES Fibers, Chisso Corp , Osaka, Japan) or sheath-core form (e g , Melty 1 M Fiber Type 4080, Unitika Ltd , Osaka, Japan)
  • side-by-side form e g , Chisso ES Fibers, Chisso Corp , Osaka, Japan
  • sheath-core form e g , Melty 1 M Fiber Type 4080, Unitika Ltd , Osaka, Japan
  • Application of heat and/or radiation to the web "cures" either type of binder system and consolidates the web
  • non-woven webs comprising macrofibers have relatively large voids Therefore, such webs have low capture efficiency of small-diameter particulate (reactive supports) which is introduced
  • the loaded webs are typically further consolidated by, for example, a calendering process
  • microfibers When the fibrous web comprises non-woven microfibers, those microfibers provide thermoplastic, melt-blown polymeric materials having active particulate dispersed therein
  • Preferred polyme ⁇ c materials include such polyolefins as polypropylene and polyethylene, pieferably further comprising a surfactant, as described in, for example, U S Patent No 4,933,229
  • surfactant can be applied to a blown microflbrous (BMF) web subsequent to web formation
  • BMF blown microflbrous
  • Polyamide can also be used Particulate can be incorporated into BMF webs as described in U S Patent No 3,971,373
  • Microflbrous webs of the present invention have average fiber diameters up to 50 ⁇ m, preferably from 2 ⁇ m to 25 ⁇ m, and most preferably from 3 ⁇ m to 10 ⁇ m Because the void sizes in such webs range fiom 0 1 ⁇ m to 10 ⁇ m, preferably from 0 5 ⁇ m to 5 ⁇ m, flow thiough these webs is not as great as is flow through the macrofibrous webs described above
  • Cast Porous Membranes Solution-cast porous membranes can be provided by methods known in the art
  • Such polymeric porous membranes can be, for example, polyolefin including polypropylene, polyamide, polyester, polyvinyl chloride, and polyvinyl acetate fibers
  • Fibrous Pulps The present invention also provides a solid phase extraction sheet comprising a porous fibrous pulp, preferably a polymeric pulp, comprising a plurality of fibers that mechanically entrap active particles, and preferably a polymeric hydrocarbon binder, the weight ratio of particles to binder being at least 13 1 and the ratio of average uncalendered sheet thickness to effective average particle diameter being at least 125 1
  • the fibers that make up the porous polymeric pulp of the SPE sheet of the present invention can be any pulpable fiber (i e , any fiber that can be made into a porous pulp)
  • Examples include polyamide fibers and those polyolefin fibers that can be formed into a pulp including, but not limited to, polyethylene and polypropylene
  • Particularly preferred fibers are aromatic polyamide fibers and aramid fibers because of their stability to both radiation and highly caustic fluids
  • useful aromatic polyamide fibers are those fibers of the nylon family Polyacrylic nitrile, cellulose, and glass can also be used Combinations of pulps can be used
  • KevlarTM DuPont, Wilmington, DE
  • Kevlar I M fiber pulps are commercially available in three grades based on the length of the fibers that make up the pulp Regardless of the type of fiber(s) chosen to make up the pulp, the relative amount of fiber in the resulting SPE sheet (when dried) ranges from about 12 5 percent to about 30 percent (by weight), preferably from about 15 percent to 25 percent (by weight)
  • Useful binders in the SPE sheet of the present invention are those materials that are stable over a range of pHs (especially high pHs) and that exhibit little or no interaction (i e , chemical reaction) with either the fibers of the pulp or the particles entrapped therein
  • Polymeric hydrocarbon materials originally in the form of latexes, have been found to be especially useful
  • Common examples of useful binders include, but are not limited to, natural rubbers, neoprene, styrene-butadiene copolymer, acrylate resins, and polyvinyl acetate
  • Preferred binders include neoprene and styrene-butadiene copolymer Regardless of the type of binder used, the relative amount of binder in the resulting SPE sheet (when dried) is about 3 percent to about 7 percent, preferably about 5 percent The preferred amount has been found to provide sheets with nearly the same physical integrity a sheets that include about 7 percent binder while allowing for as great a
  • the relative amount of particles in a given SPE sheet of the present invention is preferably at least about 65 percent (by weight), more preferably at least about 70 percent (by weight), and most preferably at least about 75 percent (by weight) Additionally, the weight percentage of particles in the resulting SPE sheet is at least 13 times greater than the weight percentage of binder, preferably at least 14 times greater than the weight percentage of binder, more preferably at least 15 times greater than the weight percentage of binder
  • the particles used in the SPE sheet of the present invention are mechanically entrapped or entangled in the fibers of the porous pulp In other words, the particles are not covalently bonded to the fibers
  • Potassium cobalt hexacyanoferrate (KCOHEX) was prepared by slowly adding an aqueous solution of 1 part 0.3 M potassium ferrocyanide in an acetic acid buffer (approximately 1.8 x 10 "3 M in acetic acid) cooled to between 0°C and 4°C at pH of between 5 and 6 to an aqueous solution of 2.4 parts 0.5 M cobalt nitrate (present in excess) cooled to between 0°C and 4°C with constant stirring.
  • KCOHEX Potassium cobalt hexacyanoferrate
  • Precipitate was separated from the reaction mixture using a centrifuge (Bird Centrifuge Model IIP200, Bird Machine Co., South Walpole, MA) by separating the initial precipitate, then repeatedly slurrying the precipitate in water and re- centrifuging, for a total of four washings Excess cobalt nitrate is pink in color, so the desired solid material was centrifuged until the supernatant liquid was no longer pink
  • Cyclone differential pressure 4 5 in H 2 O ( 1 1 43 x 1 O ' kg/cm 2 ) Recovered dried potassium cobalt hexacyanoferrate represented 92 percent yield, and was observed under an Olympus BH2 microscope (Olympus America, Inc , Melville, NY) to be spherical in shape Measurement of the particles using a Horiba Model LA-900 Particle Size Analyzer (Horiba Instruments, Inc , Irvine, CA), showed an average particle size of approximately 1 1 micrometers and a particle size distribution of from about 7 micrometers to about 60 micrometers.
  • Potassium cobalt hexacyanoferrate was prepared as described in Example 1, except that the solid precipitate obtained from the final centrifuge wash was spread out in a thin layer about 2.5 cm thick on a drying tray and heated in air at 1 10°C- 1 15°C until the solid had dried and its color had changed from green to purplish- black
  • the dried solid was subjected to cryogenic hammer-milling by means of a Model D Comminutor (Fitzpatrick Co , Elmhurst, IL) using a 325-mesh screen (0 044 mm sieve opening) and the resulting powder was sized in a hydrocyclone (Richard Mozley Ltd , Cornwall, UK).
  • Particles in the range of from about 1 to about 50 micrometers in their largest dimension were retained, with an average particle size of approximately 10- 15 micrometers Yield of sized particles was approximately 60 percent As expected from a milling process, particles were typically irregular in shape (significant deviation from spherical) and a broad particle size distribution was obtained
  • a particle-filled porous web was prepared from the spherical potassium cobalt hexacyanoferrate particles of Example 1
  • An agitated slurry of 20 g KevlarTM 1F306 dry aramid fiber pulp (DuPont, Wilmington, DE) in 2000 g water was blended in a 4 L Waring' M blender at a low speed for 30 seconds, then mixed with 0.25 g Tamol 850TM dispersant (Rohm & Haas Co , Philadelphia, PA), followed by 8.75 g (3.5 g dry weight) Goodrite l M 1800X73 styrene-butadiene latex binder aqueous slurry (B F.
  • Example 3 was repeated using ground and sized particulate as obtained in Example 2 in place of spray-dried particles Drain time was 60 seconds
  • Example 5 A 90 mm diameter disk having a thickness of 3 2 mm was die cut from the particle-filled porous web of Example 3 The disk was placed in a stainless steel disk holder (Cole Parmer Instrument Co., Niles, IL) fitted with inlet and outlet pipes, so that the effective disk diameter was 80 mm The disk was washed with water, then an aqueous solution containing 12 mg/L cesium ion was pumped first through two canister-style prefilters in series (FiltreteTM Cartridges, Memtec America Corp., Timonium, MD) then through the disk at a flow rate of 105 mL/min , which corresponds to 6 49 Bed Volumes/min , wherein Bed Volume means the volume of the disk Cesium removal, reported as C/C 0 , where C represents the cesium concentration in the effluent and C Cincinnati represents initial cesium concentration, as a function of Bed Volumes is shown in Table I The pressure drop across the membrane was found to be constant at 55 KPa throughout the evaluation

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PCT/US1996/011487 1996-03-08 1996-07-09 Adsorbent for cesium ion and method of making and using WO1997032816A1 (en)

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AU71035/96A AU7103596A (en) 1996-03-08 1996-07-09 Adsorbent for cesium ion and method of making and using
EP19960932136 EP0885169B1 (en) 1996-03-08 1996-07-09 Adsorbent for cesium ion and method of making and using
JP53173797A JP2000506827A (ja) 1996-03-08 1996-07-09 セシウムイオン用吸着剤と、その製造方法および使用方法
DE69608820T DE69608820T2 (de) 1996-03-08 1996-07-09 Adsorptionsmittel für cäsiumionen und verfahren zu ihrer herstellung

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WO1999010278A1 (en) * 1997-08-27 1999-03-04 Minnesota Mining And Manufacturing Company Adsorbent for metal ions and method of making and using
WO2006072962A1 (en) * 2005-01-10 2006-07-13 Secretary, Department Of Atomic Energy Calcium potassium ferrocyanide, a prophylactic mixture comprising this compound and the use thereof for decorporation of radiocesium in subjects affected by nuclear radiation
JP2013019882A (ja) * 2011-05-06 2013-01-31 Dainichiseika Color & Chem Mfg Co Ltd セシウム拡散防止液
JP2013019881A (ja) * 2011-05-06 2013-01-31 Dainichiseika Color & Chem Mfg Co Ltd セシウム除去材
JP2013061220A (ja) * 2011-09-13 2013-04-04 Futaba Shoji Kk 放射性セシウム吸着性布帛

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Publication number Priority date Publication date Assignee Title
WO1999010278A1 (en) * 1997-08-27 1999-03-04 Minnesota Mining And Manufacturing Company Adsorbent for metal ions and method of making and using
WO2006072962A1 (en) * 2005-01-10 2006-07-13 Secretary, Department Of Atomic Energy Calcium potassium ferrocyanide, a prophylactic mixture comprising this compound and the use thereof for decorporation of radiocesium in subjects affected by nuclear radiation
US7935366B2 (en) 2005-01-10 2011-05-03 Secretary, Department Of Atomic Energy Calcium Potassium Ferrocyanide, a prophylactic mixture comprising this compound and the use thereof for decorporation of Radiocesium in subjects affected by nuclear radiation
JP2013019882A (ja) * 2011-05-06 2013-01-31 Dainichiseika Color & Chem Mfg Co Ltd セシウム拡散防止液
JP2013019881A (ja) * 2011-05-06 2013-01-31 Dainichiseika Color & Chem Mfg Co Ltd セシウム除去材
JP2013061220A (ja) * 2011-09-13 2013-04-04 Futaba Shoji Kk 放射性セシウム吸着性布帛

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US6093664A (en) 2000-07-25
CN1214026A (zh) 1999-04-14
EP0885169B1 (en) 2000-06-07
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DE69608820T2 (de) 2000-11-16

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